DE2116500B2 - PROCESS FOR THE PREPARATION OF 1,1'-PEROXYDICYCLOHEXYLAMINE - Google Patents

Description

Patent specification 1 548 915 be a magnesium ion sodium EDTA and tetrasodium EDTA. The concentration of about 7 g / liter, that is to say about 0.7 wt. Metal salt may contain introduced anion,
However, it is preferred to use the salt in the form of a

about 0.03 to 0.08 percent by weight, calculated on the solution, without isolation of a solid, of the total metal derivative (in most cases turning 55. It may be desirable to use over only half the amount of the claimed shot of the sodium salt of EDTA at the Her-metal derivative of EDTA, and the balance consisting of disodium position of the metal salt to be used. Thus, it may EDTA is), Peroxyaminausbeuten be desirable from 88 to, an amount of sodium salt of 96 _^0/0, compared to only 83 to 86% One must use EDTA in addition, which is an excess up to impure product when using the disodium 60 150 weight percent compared to the stoichiometric EDTA alone. This represents an increase in the yield in the case of an amount, for example up to 100 ⁿ / “. The stoichi · simultaneous considerable reduction in the usemetric amount corresponds to 1 gram atom of metal on application concentration in comparison to the magnesium 1 gram molecule sodium salt of EDTA. The oversalt of the EDTA is surprising. In particular, the use of an excess of the sodium salt from the prior art does not offer the person skilled in the art any EDTA can help stabilize the metal salt against indications that the observed yield hydrolysis is stabilizing.

Achieve increase with the claimed process It may be desirable in manufacturing

would let. from solutions of metal salts to alkaline solutions

either by preparing the metal salts in an alkaline medium or by making the solution alkaline after preparation. The solution of the metal salts can, for. B. have a pH of 5 to 12. Therefore, it is preferred, when reacting cyclohexanone, hydrogen peroxide and ammonia, to supply the metal salt in the ammonia fed in, although it can also be introduced in one of the other two reactants. It is believed that the use of an alkaline solution increases the stability of the metal salts, although the use of a very alkaline solution, e.g. B. with a pH greater than 9, in the case of some metal salts, e.g. B. in the case of aluminum derivative, the extent of hydrolysis which takes place can increase. Examples of suitable metal salts of EDTA which can be used in the process of the invention in addition to aluminum or lanthanum derivatives are zinc, cadmium and nickel derivatives. Mixtures of two or more such mer ill derivatives can also be used. The examples illustrate the invention.

Manufacture of metal derivatives of EDTA
Nickel derivative

6.2 g of basic nickel carbonate (NiCO ₃ · 2 Ni (OH), · 4H ₂ O) and 37.2 g of disodium EDTA (100% excess) were added together to 300 ml of water and the mixture was allowed to stir for 15 to 30 minutes heated at 40 ° C. A solution of the nickel derivative was obtained.

Aluminum derivative

19 g of aluminum nitrate (A1 (NO ₃ ) ₃ · xH ₂ O; about 59% A1 (NO ₃ ) ₃ ) and 37.2 g of disodium EDTA (100% excess) were added together to 400 ml of water (the complex appears to be more water-soluble than Na ₂ -EDTA) and the mixture was heated with occasional shaking or stirring at 40 ° C for 15 to 30 minutes. The solution was brought to a pH of 8 to 9 (by approximately 20 ml of ammonia 0.880).

Zinc derivative

11 g of zinc acetate (Zn (OAc) ₃ · 2 Η, Ο) and 37.2 g of disodium EDTA (100% excess) were added to 100 ml of water and the solution was purified by means of ammonia (e.g. about 50 ml ammonia 0.880) made alkaline.

Lanthanum derivative

ίο 4.3 g of lanthanum nitrate (La (NO ₃ ) ₃ · 6 H ₂ O) and 6.7 g of disodium EDTA (100% excess) were added together to 100 ml of water and the solution was made alkaline with ammonia.

Cadmium derivative

5.4 g of cadmium acetate (Cd (OAc), · 2 H ₂ O) and 13.4 g of disodium EDTA (100% excess) were added to 200 ml of water and the solution was made alkaline with ammonia.

Effect of individual aluminum and lanthanum derivatives of EDTA on the yields of peroxyamine

Examples 1 to 8c

Cyclohexanone (2.13 mol / hour), aqueous ammonia solution (e.g. 0.880; 2.8 mol NH ₃ / hour) and hydrogen peroxide solution (39% w / v; 1.13 mol H ₂ O »/ hour) were pumped continuously via separate feed lines to a continuous two-stage, stirred, cascade reactor system.

The catalyst (16 ° ₀ w / v, based on the ammonia fed in) was introduced into the reaction system in the ammonia fed in. The stabilizer was introduced into either the ammonia fed or the peroxide fed; different types of stabilizers have been used at different concentrations. The details can be found in Table I.

Both reactors were kept at 30 ^° C. and the levels were adjusted to give a total residence time of 9 hours. The yields achieved are shown in Table 1.

Table I.

Effect of individual derivatives of EDTA on the yields of 1,1'Peroxydicyclohexyl In all experiments, nine hours dwell time at 3O ⁰ C

example
No. Aluminum / Na ₂ -EDTA Stabilis
catalyst
(Ammonium salt) ator
The reac
gate supplied
in Excess
Na _s EDTA
(° / o) Amount in
overall
feed
(° / o) Yield to
Peroxyamine
(° / o) Cyclo-
hexanone
Balance sheet
( ⁰ A,) 1 Aluminum / Na ₂ -EDTA nitrate NH ₄ OH 100 0.03 96 99 2 Lanthanum / Na ₂ EDTA nitrate NH ₄ OH 100 0.07 93 100 3 Aluminum / Na ₂ -EDTA nitrate NH ₄ OH 100 0.08 88 99.5 4th Aluminum / Na ₂ -EDTA nitrate NH ₄ OH no 0.08 90 98.7 5 Aluminum / Na ₂ -EDTA chloride NH ₄ OH 100 0.08 90 99 6th Na ₂ -EDTA acetate NH ₄ OH 100 0.08 89 7c Na ₂ -EDTA acetate NH ₄ OH 100 0.08 <83 *) - 8c acetate H ₂ O ₂ 100 0.08 <86 *) -

c = comparative example.
*) very impure product.

Effect of mixed aluminum and lanthanum derivatives
of EDTA on the yields of Ι, Γ-peroxydicyclohexylam

Examples 9-11

The procedure of Examples 1 to 8c was repeated with the exception that derivative of EDTA was used and the catalyst in all of these examples. All details and the results of the experiments are shown in Table II.

Table 11 example

No.

Mixed metal derivative

from EDTA (fed into

Ammonia solution)

a lot of
Complex in the
entire feed (", ·")

Yield of peroxyamine (

Base titration

Todorm Ana

9
10
11

1: 1 Al Zn complex 1: 1 Al '/ Ni complex 1: 1 AI / Cd complex

0.08
0.08
0.0S

89.1
91.7

Claims (1)

The CvclohexanoD, hydrogen peroxide and am- Claim: moniak can cover a moderately wide range of Conditions brought together to implement Process for the preparation of 1,1'-peroxy be. The molar ratio of cyclohexanone dicyclohexylamine by converting cyclo-5 to hydrogen peroxide is preferably approximately hexanone with hydrogen peroxide and ammonia 2: 1, is z. B. between 2.1: 1 and 1.9: 1, while in the presence of a metal derivative of ethylene - the molar ratio of ammonia to hydrogen diamine tetraacetic acid, this means that peroxide is at least 1: 1, preferably about 3: 1 draws that the implementation matters in the present. of an aluminum or lanthanum derivative from io The reaction between cyclohexanone, ethylenediaminetetraacetic acid takes place, either hydrogen peroxide and ammonia can be carried out over a temperature range alone or in conjunction with zinc, nickel or moderately wide, cadmium derivatives of ethylenediamine tetraacetic - e.g. in the range of 20 up to 60 ⁰ C, especially at 30 acid is used. up to 5O ⁰ C. 15 The amount of the metal derivative of ethylenediaminetetraacetic acid in the reaction mixture can be over vary over a wide range, e.g. B. of about 0.005 to about 1 percent by weight, based on the total reaction mixture, preferably from about 0.01 to 20 about 0.2 percent by weight, based on the entire production of Ι, Ι'-peroxydicyclohexylamine reaction mixture. by reactions of cyclohexanone with hydrogen The reaction can be carried out in the presence of a catalyst peroxide and ammonia are known. Run from the British sators, e.g. B. in the presence of From patent specification 1198 421 it is known to convert this to ammonium nitrate, ammonium chloride or from ameetting in the presence of a sodium salt of 25 monium or metal salts of organic carboxylic acids, Ethylenediaminetetraacetic acid (EDTA). the I. group of the periodic table, for example Furthermore, from the French patent specification ammonium acetate. 1 548 915 the use of the magnesium salt of The reaction time can widen over a moderately EDTA is known for this purpose. In both cases the range will vary and the optimal time will depend on it however, there are quite large amounts of the EDTA salts 30 of the temperature and of the applied temperature required to get the best yields of Ι, Γ-peroxy catalyst. Examples of suitable times are 1 to dicaclohexylamine to achieve. It would be a great 20 hours. So with continuous Um-values, if one were able to add an additive, total reaction times of 4 to 12 hours to use, which are used in smaller amounts than that. ! Sodium and magnesium salts of EDTA are effective 35 The reaction can take place in any suitable is full. Way to be carried out, e.g. B. by According to the invention, it is a process of mixing the reaction tensioners in one or more for the production of l, l'-Peroxydicyclohe \ ylamin stirred containers. by reacting cyclohexanone with hydrogen. The EDTA metal derivatives used peroxide and ammonia in the presence of a metal 40 occurs in the reaction to the formation of derivatives of ethylenediaminetetraacetic acid, the da- Ι, Γ-peroxydicyclohexylamine required no time is characterized in that the reaction enters into marked hydrolysis. Presence of an aluminum or lanthanum derivative. B. produced thereby of ethylenediaminetetraacetic acid, which can be derived from being a salt of the metal and a sodium, either alone or in conjunction with the zinc, nickel 45 salt of EDTA mixed together in solution. Examples or cadmium derivatives of ethylenediaminetetra- suitable salts are the carbonate, the nitrate and the acetic acid is used. Acetate. While in the method of the French The sodium salts of EDTA can, for. B. Di-